18085-02-4

Basic information

• Product Name: 3,4-DIACETOXY-1-BUTENE
• Synonyms: 3,4-DIACETOXY-1-BUTENE;3-BUTENE-1,2-DIOL DIACETATE;DACB;3,4-DIACETOXY-1-BUTENE, 99.5+%;Vinylglycoldiacetate;3,4-DIACETOXY-1-BUTENE 97%;1,2-diacetoxybut-3-ene;3-Butene-1,2-diol diacetate, DAcB
• CAS NO: 18085-02-4
• Molecular Formula: C₈H₁₂O₄
• Molecular Weight: 172.18
• EINECS: 421-720-5
• Product Categories: Intermediates;Miscellaneous Reagents
• Mol File: 18085-02-4.mol

Chemical Properties

• Boiling Point: 95-96 °C10 mm Hg(lit.)
• Flash Point: 196 °F
• Appearance: /
• Density: 1.059 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.182mmHg at 25°C
• Refractive Index: n20/D 1.43(lit.)
• Storage Temp.: -20°C Freezer, Under inert atmosphere
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• PKA: 5.1[at 20 ℃]
• Water Solubility: 26.2g/L at 25℃
• CAS DataBase Reference: 3,4-DIACETOXY-1-BUTENE(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-DIACETOXY-1-BUTENE(18085-02-4)
• EPA Substance Registry System: 3,4-DIACETOXY-1-BUTENE(18085-02-4)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• WGK Germany: 1
• Hazardous Substances Data: 18085-02-4(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
3,4-Diacetoxy-1-butene is used as an intermediate in the preparation of 1,4-butanediol and tetrahydrofuran, which are important organic compounds with various applications in the chemical industry.
Used in Catalyst Technology:
3,4-Diacetoxy-1-butene is used in the method for isomerization of allyl compounds using gold or platinum catalysts, which is an important process in the synthesis of various organic compounds.
Used in the Chemical Industry:
3,4-Diacetoxy-1-butene is used as a chemical intermediate for the production of various chemicals and materials, contributing to the development and advancement of the chemical industry.

Flammability and Explosibility

Notclassified

InChI:InChI=1/C8H12O4/c1-4-8(12-7(3)10)5-11-6(2)9/h4,8H,1,5H2,2-3H3/t8-/m1/s1

Upstream product

• 930-22-3 epoxybutene 
• 108-24-7 acetic anhydride 
• 497-06-3 3,4-butenediol 
• 75-36-5 acetyl chloride 
• 106-99-0 buta-1,3-diene 
• 64-19-7 acetic acid 
• 2570-63-0 thallium(III) triacetate 
• 25260-60-0 cis-1,4-bis(acetyloxy)but-2-ene 
• 821-06-7 (E)-1,4-dibromobutene 
• 127-09-3 sodium acetate 
• 1576-98-3 trans-1,4-diacetoxy-2-butene 
• 31469-25-7 1,1-bis(trimethylsiloxy)-2-methylprop-1-ene 
• 189162-38-7 acetoxybut-2-enyl trichloroacetimidate 
• 1576-98-3 1,4-diacetoxybut-2-ene 

Downstream Products

• 89543-93-1 Acetic acid 2-acetoxy-1-(3-phenyl-4,5-dihydro-isoxazol-5-yl)-ethyl ester 
• 16939-73-4 (E)-2-heptenyl acetate 
• 83540-70-9 (Z)-2-Hepten-1-yl acetate 
• 7553-56-2 iodine 
• 1151782-09-0 (E)-4-(4-fluorophenyl)but-3-ene-1,2-diyl diacetate 
• 119420-99-4 (E)-4-phenylbut-3-ene-1,2-diyl diacetate 
• 1151782-08-9 (E)-4-(4-bromophenyl)but-3-ene-1,2-diyl diacetate 
• 1182278-41-6 (E)-4-(4-chlorophenyl)but-3-ene-1,2-diyl diacetate 
• 1182278-37-0 (E)-4-(4-methoxyphenyl)but-3-ene-1,2-diyl diacetate 
• 1182278-38-1 (E)-4-p-tolylbut-3-ene-1,2-diyl diacetate 
• 1182278-47-2 (E)-4-(2-methoxyphenyl)but-3-ene-1,2-diyl diacetate 
• 1182278-46-1 (E)-4-(3-nitrophenyl)but-3-ene-1,2-diyl diacetate 
• 1182278-44-9 (E)-4-(4-iodophenyl)but-3-ene-1,2-diyl diacetate 
• 1257322-07-8 dimethyl-1-(4-methylphenylsulfonyl)-3-vinyl-2,3-dihydroquinoline-4,4(1H)-dicarboxylate 

Relevant articles and documents

Process for preparation of 4-acetoxy-2-methyl-2-butene-1-aldehyde and intermediates thereof

The invention relates to the technical field of organic synthesis, and discloses a method for preparing 4-acetoxy-2-methyl-2-butene-1-aldehyde and an intermediate thereof. The method comprises the following steps: (1) in the presence of an esterification reagent, carrying out esterification reaction on 1, 4-butenediol to obtain 1, 4-butenediol diacetate; (2) in the optional presence of a first catalyst, carrying out an isomerization reaction on the 1, 4-butenediol diacetate to obtain 3, 4-diacetoxy-1-butene; (3) in the presence of a phosphorus-containing ligand and a rhodium catalyst and/or a cobalt catalyst, carrying out hydroformylation reaction on the 3, 4-diacetoxy-1-butene, carbon monoxide and hydrogen to obtain 2-methyl-3, 4-diacetoxy-1-butyraldehyde; (4) in the optional presence of a third catalyst, carrying out an elimination reaction on the 2-methyl-3, 4-diacetoxyl-1-butyraldehyde to obtain the 4-acetoxyl-2-methyl-2-butene-1-aldehyde. The method provided by the invention has the advantages of mild reaction conditions, environmental friendliness and high yield.

Preparation method of 3,4-diacetoxy-1-butene

The invention discloses a preparation method of 3,4-diacetoxy-1-butene. The preparation method comprises steps as follows: an esterification step: 1,4-butylene glycol and acetic acid are subjected to an esterification reaction in the presence of acid, a solution containing 1,4-diacetoxy-2-butene and acetic acid is obtained, acetic acid is removed and 1,4-diacetoxy-2-butene is obtained; an isomerization step: cuprous catalysts are added to 1,4-diacetoxy-2-butene obtained in the esterification step, the mixture is heated for an isomerization rearrangement reaction, and a mixed solution containing 3,4-diacetoxy-1-butene is obtained; a purification step: the mixed solution obtained in the isomerization step is purified, and 3,4-diacetoxy-1-butene is obtained. The preparation method adopts easy-to-realize reaction conditions and has the characteristic of high yield.

METHOD FOR ISOMERIZING ALLYL COMPOUND

Catalyst for isomerization of allyl compound in method, catalyst by restraining degradation caused, low catalyst levels usage in high yield isomer make it possible to obtain a an industrially advantageous method provides for isomerization of allyl compounds. In the presence of catalyst, raw material allyl compound corresponding allyl compound as isomerizing method, before isomerization using catalyst raw material allyl compounds organic phosphorus compound-containing solution is characterized by contacting the isomerization method.

PROCESS FOR PRODUCING ESTER COMPOUND HAVING a,?-UNSATURATED BOND

A process for producing an α,β-unsaturated bond-containing ester compound, comprising: reacting an internal olefin or a cyclic olefin having one carbon-carbon double bond or more at a position other than terminals of a molecule thereof (the internal olefin and the cyclic olefin may each contain a hetero atom) with a carboxylic acid in an amide-based solvent in the presence of a palladium catalyst, a base, and molecular oxygen, thereby bonding a carboxyl group of the carboxylic acid to at least one of carbon atoms constituting the carbon-carbon double bond and carbon atoms at allylic positions of the internal olefin or the cyclic olefin, to obtain an ester compound having an α,β-unsaturated bond, the amide-based solvent being represented by the following formula (1): (in the formula (1), R1 represents an alkyl group having 1 to 4 carbon atoms; R2 and R3 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group; and when R1 and R2 are alkyl groups, R1 and R2 may be bonded to each other to form a ring structure).

Catalytic asymmetric synthesis of chiral allylic esters

A broadly useful catalytic enantioselective synthesis of branched allylic esters from prochiral (Z)-2-alkene-1-ols has been developed. The starting allylic alcohol is converted to its trichloroacetimidate intermediate by reaction with trichloroacetonitrile, either in situ or in a separate step, and this intermediate undergoes clean enantioselective SN2′ substitution with a variety of carboxylic acids in the presence of the palladium(II) catalyst (Rp,S)-di-μ-acetatobis[(η5- 2-(2′-(4′-methylethyl)oxazolinyl)cyclopentadienyl-1-C,3′-N) (η4-tetraphenylcyclobutadiene)cobalt]dipalladium, (R p,S)-[COP-OAc]2, or its enantiomer. The scope and limitations of this useful catalytic asymmetric allylic esterification are defined.

Method of Producing 3,4-Diacyloxy-1-Butene

This invention provides a method of producing 3,4-diacyloxy-1-butene by isomerization by heating 1,4-diacyloxy-2-butene in the presence of an isomerization catalyst, with a higher yield rate with respect to the supply amount of a starting material, even not changing a kind of the isomerization catalyst, a composition of the starting material, and/or a chemical structure of 1,4-diacyloxy-2-butene used as the starting material. This advantage is achieved by preventing the isomerization from terminating through suppressing attaining equilibrium. The isomerization is conducted while distilling away 3,4-diacyloxy-1-butene (the isomerized product) with use of a reactor equipped with a distillation device. The isomerization is preferably carried out under heating to a temperature of not less than the boiling point of 3,4-diacyloxy-1-butene. Also, the isomerization is preferably carried out under a reducing pressure. Further preferably, 1,4-diacyloxy-2-butene is continuously supplied and 3,4-diacyloxy-1-butene is continuously distilled away during isomerization.

Expeditious formation of γ-lactones upon palladium-catalyzed double nucleophilic addition of bis(TMS)ketene acetals to vicinal allylacetates

Polysubstituted γ-lactones are easily obtained, in one step, upon the interaction of bis(TMS)ketene acetals with vicinal allylic acetates in the presence of catalytic amounts of Pd(PPh3)4.

Palladium(II)-catalyzed isomerization of (Z)-1,4-diacetoxy-2-butene: Solvent effects

The isomerization of (Z)-1,4-diacetoxy-2-butene (1) catalyzed by PdCl 2(MeCN)2 was studied in THF and DMF. The reaction occurs more rapidly in THF than in DMF, but in both solvents it did not proceed to complete consumption of the substrate and led to a mixture of 1, (E)-1,4-diacetoxy-2-butene (2), and 1,2-diacetoxy-3-butene (3). The formation of 2 is more favored in DMF than in THF. The reactivity of 1 and the solvent effect differ strongly from those previously obtained with Pd(PPh 3)4 as the catalyst. Interpretations are provided for the crucial role of the nature of both solvent and intermediates on the course of the isomerizations. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Palladium(0)-catalyzed isomerization of (Z)-1,4-diacetoxy-2-butene - Dependence of η1- or η3-allylpalladium as a key intermediate on the solvent polarity

In the presence of Pd(PPh3)4, (Z)-1,4-diacetoxy-2-butene is selectively isomerized to (E)-1,4-diacetoxy-2-butene in THF while both (E)-1,4-diacetoxy-2-butene and 1,2-diacetoxy-3-butene are obtained in DMF. Evidence to support the involvement of an η1-allylpalladium in the former solvent and of a cationic η3-allylpalladium in the latter as the keys intermediates is presented.

A new class of oxygen nucleophiles for regioselective 1,4-addition to butadiene monoxide catalyzed by palladium complexes

Butadiene monoxide reacts with high regioselectively with anhydrides to give preferentially diesters of 2 buten-1,4-diol in presence of palladium phosphine complexes. Reaction regioselectivity is strongly influenced by the nature of palladium ligand, anhydride and solvent.